Apple Anthocyanins: Identification of Cyanidin-7-Arabinoside

SUMMARY— The anthocyanin pigments of Red Delicious apples were isolated and identified from their chromatographic, spectral and chemical properties. The maior pigment was cyanidin-3-galactoside. The minor pigments were cyanidin-3-arabinoside and cyanidin-7-arabinoside. Cyanidin-7-arabino-side was isolated from a natural source for the first time. Three pigments were isolated from 74 varieties of apples, two from six varieties and only one from two varieties.     

云南丽江和吉林靖宇11种越橘果实花色苷组分的分析

采用高效液相色谱法对云南丽江、吉林靖宇11种越橘果实花色苷组分进行测定。通过标准品的分析,建立了飞燕草素-3-半乳糖苷、飞燕草素-3-葡萄糖苷、矢车菊素-3-半乳糖苷、矢车菊素-3-葡萄糖苷、锦葵色素-3-半乳糖苷、锦葵色素-3-葡萄糖苷的回归方程,相关系数为0.9939~0.9968,精密度RSD为2.00%~3.73%,回收率在98.90%~100.99%,方法准确可行。通过6种标准品的对比,供试的15个样品中,所有越橘品种均有飞燕草素-3-半乳糖苷、矢车菊素-3-半乳糖苷、锦葵色素-3-半乳糖苷3种花色苷,飞燕草素-3-半乳糖苷平均含量为223.99 μg/g、锦葵色素-3-半乳糖苷平均含量为153.34 μg/g,二者占总花色苷的65%。采用欧氏距离聚类分析表明,集群1为飞燕草素-3-半乳糖苷含量较高的三种越橘,代表品种为丽江雷戈西、丽江奥尼尔、靖宇杜克;集群2为6种花色苷总含量较高的越橘品种,代表品种为丽江北陆与靖宇早蓝,说明飞燕草素-3-半乳糖苷含量与花色苷总含量是评价越橘花色苷特点的重要因子。     

蔓越莓花色苷的组成鉴定及抗氧化能力

对蔓越莓花色苷的组成进行鉴定,并对其抗氧化能力进行测定。采用pH示差法测定花色苷提取量,超高压辅助提取蔓越莓花色苷含量为（75.49±0.43）mg/100?g,常规溶剂提取蔓越莓花色苷含量为（67.31±1.08）mg/100?g,蔓越莓中总花色苷含量为（79.52±0.50）mg/100?g;选择AB-8大孔树脂对蔓越莓花色苷粗提物进行纯化,冻干粉中花色苷含量从（46.10±0.92）mg/g提高到（309.26±2.37）mg/g。通过测定1,1-二苯基-2-三硝基苯肼自由基清除率、2,2’-联氮基-双-（3-乙基苯并噻唑啉-6-磺酸）二铵盐自由基清除能力和总抗氧化能力,比较蔓越莓花色苷与VC的抗氧化能力。结果表明：同质量浓度条件下,蔓越莓花色苷的抗氧化能力强于VC。通过高效液相色谱-质谱联用技术在蔓越莓中鉴定出7?种花色苷：芍药素-3,5-二己糖苷、矢车菊素-3-半乳糖苷、矢车菊素-3-葡萄糖苷、矢车菊素-3-阿拉伯糖苷、芍药素-3-半乳糖苷、芍药素-3-葡萄糖苷、芍药素-3-阿拉伯糖苷,其中芍药素-3,5-二己糖苷首次在蔓越莓中被鉴定出。     

Stability of Anthocyanins in the Skin of Starkrimson Apples Stored Unpackaged, Under Heat Shrinkable Wrap and In-Package Modified Atmosphere

The concentration of cyanidin-3-galactoside, cyanidin-3-arabinoside, and an unidentified cyanidin arabinoside in the skin of Starkrimson apples stored unpackaged, under in-package modified atmosphere and in heat shrinkable wrap were determined at 7, 23, and 30 weeks storage. Carbon dioxide levels of higher than 73% in in-packaged modified atmosphere severely destablized the three anthocyanins. The unidentified cyanidin arabinoside was the most stable anthocyanin in the skin of Starkrimson apples. Cyanidin-3-galactoside was more stable in the skin of unpackaged apples than shrink-wrapped apples.     

龙葵果花色苷的分离与鉴定

采用硅胶柱层析技术分离制备龙葵果花色苷。分离得到的2 个花色苷馏分经紫外-可见光谱、高效液相色谱-电喷雾串联质谱（high performance liquid chromatography electrosprary ionization-mass spectrometry,HPLC-DADESI-MS/MS）进行结构鉴定,并结合酸水解分析糖苷种类。最终确定馏分Ⅰ为飞燕草素-3-琥珀酰阿拉伯糖苷,根据峰面积归一化法计算其纯度为94%;馏分Ⅱ为矢车菊素-3-半乳糖苷和矢车菊素-3-乙酰半乳糖苷,峰面积归一化法计算其纯度分别为45.67%和13.97%。     

Changes of flavonoid content and antioxidant capacity in blueberries after illumination with UV-C

The levels of flavonoids in blueberries (Vaccinium corymbosum L.) were found to increase after illumination with UV-C. Phytochemicals affected included resveratrol, myricetin-3-arabinoside, quercetin-3-galactoside, quercetin-3-glucoside, kaempferol-3-glucuronide, delphinidin-3-galactoside, cyanidin-3-galactoside, delphinidin-3-arabinoside, petunidin-3-galactoside, petunidin-3-glucoside, petunidin-3-arabinoside, malvidin-3-galactoside, malvidin-3-arabinoside, and chlorogenic acid as analyzed by HPLC. Significantly higher antioxidant capacity was detected in fruit treated with 2.15, 4.30, or 6.45 kJ m⁻² compared to the control fruit. UV-C dosage of 0.43 kJ m⁻² also increased phenolics and anthocyanins, but to a lesser extent. The optimum doses of UV-C for enhancing phytochemical content in blueberries were 2.15 and 4.30 kJ m⁻². These data suggest that proper use of UV-C illumination is capable of modifying the phytochemical content of blueberries. Time course measurements of the effects of UV-C revealed that the strongest responses of fruit to UV-C treatment occurred instantly after the illumination and the effects diminished with time. Therefore, even though residual effects were evident following UV-C exposure, the best results were obtained immediately after the treatment.     

Lingonberry (Vaccinium vitis-idaea L.) grown in the Pacific Northwest of North America: Anthocyanin and free amino acid composition

Lingonberries and their products are popular and generally accessible in Europe, though in the US they are uncommon and considered a minor berry/fruit crop. The on-going interest in potential health benefits from berry consumption has heightened interest in broadening the selection of berry/fruit crops in the US. This study measured total phenolics, total tannins, complete anthocyanin content, and total (and individual) free amino acid composition for each of five lingonberry cultivars. Cultivars Ida, Koralle, Linnea, Sanna, and Sussi were grown in Oregon, USA, and had only been evaluated previously for their horticultural traits. All five cultivars contained the three anticipated anthocyanins (by HPLC): cyanidin-3-galactoside (main anthocyanin found in these berries), cyanidin-3-glucoside, and cyanidin-3-arabinoside. These lingonberries’ total anthocyanin content ranged from 27.4 (‘Linnea’) to 52.6 (‘Ida’) mg/100 g fw. They contained 22 free amino acids (FFAs) and total FAAs ranged from 28.92 (‘Sanna’) to 70.38 (‘Koralle’) mg/100 g fw. Asparagine (ASN) was the leading FAA (22–34% of the total FAAs) for all five cultivars. This is the first report on lingonberry FAA content.     

Retention of Antioxidant Capacity of Vacuum Microwave Dried Cranberry

ABSTRACT: In this study, cranberries were dried by vacuum-microwave drying (VMD), freeze-drying (FD), or hot air-drying (AD), to compare the effects of different drying processes on both physical changes as well as the retention of bioactive components in dried samples. Total porosity (%) and average pore radius of dehydrated cranberries were greater using VMD compared to FD and AD (P < 0.05). Crude methanol cranberry powdered extracts were fractionated by solid phase extraction (SPE) into organic acid-, total phenolics-, anthocyanin-, or proanthocyanidin-enriched extracts, respectively. The chemical composition of the 60% acidified methanol fractions contained cyanidin-3-galactoside, cyanidin-3-arabinoside, peonidin-3-galactoside, and peonidin-3-arabinoside, as assessed by HPLC. Antioxidant activities of cranberry fractions were measured using chemical ORAC and ABTS methods. The 60% acidified methanol fraction had a significantly higher (P < 0.05) antioxidant potential than the other chemical fractions, which was largely attributed to the relatively higher anthocyanin content. In general, vacuum-microwave drying and freeze-drying resulted in similar retention of anthocyanins and antioxidant activity, which were both relatively higher (P < 0.05) than that recovered from cranberries dried by hot air drying.     

西伯利亚白刺果实花色苷的初步鉴定

以西伯利亚白刺果实为材料,利用光谱方法和色谱方法对其花色苷进行了初步鉴定。结果表明：西伯利亚白刺果实花色苷中1号色素为天竺葵色素-3-葡萄糖鼠李糖苷,3号色素为矢车菊色素-3-葡萄糖鼠李糖苷,4号色素为飞燕草色素-3-半乳糖苷。     

Flavonoids, sugars and fruit acids of alpine bearberry (Arctostaphylos alpina) from Finnish Lapland

Alpine bearberry (Arctostaphylos alpina L.) is a special circumpolar edible berry primarily used for household purposes but with greater potential in commercial applications than utilized thus far. In this study, the flavonoids of alpine bearberry were investigated with HPLC-DAD and HPLC-MS, and the sugars and fruit acids as trimethylsilyl derivates with GC-FID. The most abundant anthocyanin was cyanidin-3-O-galactoside accounting for over 95% of the anthocyanins. Eight other anthocyanins existed in trace amounts only, the richest of them being cyanidin-3-O-arabinoside and cyanidin-3-O-glucoside. Cyanidin accounted for over 99% of the anthocyanin aglycones. All the flavonols identified were glycosides of quercetin. Majority of the sugars were glucose and fructose while the most abundant fruit acid was quinic acid. The unique anthocyanin composition of alpine bearberry encourages advanced use of the berry as a food ingredient in private households and in industrial applications. In addition, it serves as a unique reference material for research purposes.     

Saskatoon berries (Amelanchier alnifolia Nutt.) scavenge free radicals and inhibit intracellular oxidation

Two cultivars (Thiessen and Smoky) of Saskatoon berries (Amelanchier alnifolia Nutt.) possess free radical scavenging activities in a concentration-dependent manner, whereas Thiessen presented higher (p < 0.05) activity compared to Smoky due to its relatively abundant anthocyanin content. Total anthocyanin content significantly corresponded to free radical scavenging activities (p < 0.05). Solvent fractionation revealed that the free radical scavenging components, i.e., anthocyanin, predominantly occurred in the ethyl acetate and n-butanol extracted fractions, suggesting that active components are more likely to occur in glycoside forms. HPLC further confirmed the existence of cyanidin-3-O-galactoside and cyanidin-3-O-glucoside as leading anthocyanins in the Saskatoon berries. Furthermore, Saskatoon berries extracts from both cultivars suppressed peroxy-radical induced intracellular oxidation in a concentration-dependent manner without affecting cell viability. The obtained results provided useful information for the future application of Saskatoon berries in the nutraceutical industry.     

Anthocyanins in cowpea [Vigna unguiculata (L.) Walp. ssp. unguiculata]

The aim of this study was to isolate and identify the anthocyanins in the black seed coated cowpea [Vigna unguiculata (L.) Walp. ssp. unguiculata] using reverse phase C-18 open column chromatography and high performance liquid chromatography (HPLC) with diode array detection and electro spray ionization/mass spectrometry (DAD-ESI/MS) analysis, respectively. Anthocyanins were extracted from the coat of black cowpea with 1% trifluoroacetic acid (TFA) in methanol, isolated by RP-C-18 column chromatography, and their structures elucidated by 1D and 2D nuclear magnetic resonance (NMR) spectroscopy. The isolated anthocyanins were characterized as delphinidin-3-O-glucoside (2) and cyanidin-3-O-glucoside (4). Furthermore, 5 minor anthocyanins were detected and identified as delphinidin-3-O-galactoside (1), cyanidin-3-O-galactoside (3), petunidin-3-O-glucoside (5), peonidin-3-O-glucoside (7), and malvidin-3-O-glucoside (8) based on the fragmentation patterns of HPLC-DADESI/MS analysis.     

ANTHOCYANIN PIGMENTS OF SOUR CHERRIES

Fresh fruits of tart cherries (Prunus cerasus L. var. Montmorency) were extracted with acidic methanol. The anthocyanin pigments were isolated and purified by conventional paper chromatography. They were identified by spectral and R_f data and by acid hydrolysis. The pigments were cy anidin-3-glucosylrutinoside, cyanidin-3-glucosylsambubioside, cyani-din-3-sophoroside, cyanidin-3-rutinoside, cyanidin-3-glucoside and peoni-din-3-rutinoside. No free cyanidin or peonidin was found. Cyanidin-3-glucosylsambubioside, reported in cherries for the first time, was also found in the varieties of English Morello, Early Richmond and Meteor     

Anthocyanins of Asparagus

SUMMARY— Four anthocyanin pigments were isolated from asparagus spears, Asparagus officinalis L., and identified by chromatographic, spectral, and chemical properties. The major pigment was a linear triglycoside, cyanidin-3-rhamnosylgluco-sylglucoside, followed by cyanidin-3-rhamnosylglucoside. The peonidin analogues of the above pigments were also present in minor quantities.     

Anthocyanin profile of mayhaw (Cretaegus opaca)

Mayhaw samples (Elite 2001, Texas Star 2000 and 1999) were harvested over a three-year period and analyzed for anthocyanin concentration, colour density, polymeric colour, and % polymeric compounds. Anthocyanins were separated by HPLC. All mayhaw samples from the three year period contained about 50% of cyanidin-3-glucoside, 10–21% cyanidin-3-galactoside, and less than 32% unidentified anthocyanins. The highest concentration of anthocyanins was detected in the Texas Star 1999 sample (about 7 mg/100 g) whereas Texas 2000 and Elite 2001 had 3.3 and 2.3 mg/100 g of anthocyanins, respectively. Colour density was lower in the Elite samples than the Texas. The polymeric anthocyanins and polymeric colour decreased in the Elite 2001 > Texas Star 2000 > Texas Star 1999 and the decrease was tentatively ascribed to sample age.     

Anthocyanin characterization and bioactivity assessment of a dark blue grained wheat (Triticum aestivum L. cv. Hedong Wumai) extract

Defatted bran of dark blue grained wheat (Triticum aestivum L., cv. Hedong Wumai) was extracted using ethanol and chemically characterized by HPLC and ESI-MS. Cyanidin-3-glucoside was the predominant anthocyanin in the pigmented wheat which also contained cyanidin-3-galactoside, pelargornidin-3-glucoside, and peonidin-3-glucoside. Ferulic acid was identified as the major simple phenolic acid, with lesser amounts of p-hydroxybenzoic acid, caffeic acid, syringic acid and p-coumaric acid also present. Anthocyanins were separated from phenolic acids using solid phase extraction, and respective fractions were determined for DPPH radical, ABTS radical scavenging tests as well as oxygen radical absorption assay. Results showed that 69% of the overall free radical scavenging capacity of dark blue grained wheat was attributed to the anthocyanin content, compared to 19% for the extractable phenolic acids. In cell based models, the pigmented wheat extract significantly suppressed both hydrogen peroxide-induced intracellular oxidation (p < 0.01) and bacterial lipopolysaccharide-induced nitric oxide (p < 0.05) production. These data report for the first time the major phytochemical composition of pigmented grained wheat and associated bioactivity towards free radical scavenging and suppression of ROS and RNS activity.     

Influence of Dekkera bruxellensis on the contents of anthocyanins,organic acids and volatile phenols of Dão red wine

The anthocyanin, organic acid and volatile phenol compositions of red wine obtained from Touriga Nacional grapes growing in the Dão region (Portugal) were determined by HPLC/DAD, HPLC/UV and GC/FID, respectively. By these means, nine anthocyanic compounds (malvidin-3,5-O-diglucoside, cyanidin-3-O-galactoside, cyanidin-3-O-glucoside, peonidin-3-O-glucoside, malvidin-3-O-glucoside, delphinidin, cyanidin, pelargonidin and malvidin), six organic acids (ketoglutaric, tartaric, malic, quinic, lactic and shikimic acids) and two volatile phenols (4-ethylguaiacol and 4-ethylphenol) were identified and quantified. Malvidin-3-O-glucoside, the pair lactic plus shikimic acids and 4-ethylguaiacol were the main anthocyanin, organic acids and volatile phenol, respectively. The effects of nine different Dekkera bruxellensis strains on these chemical parameters were also evaluated. The results obtained indicate that some strains of D. bruxellensis yeast are able to cause deterioration of red wine from the Dão region during its maturation by the production of volatile phenols, namely 4-ethylphenol.     

Characterisation of anthocyanins in the black soybean (Glycine max L.) by HPLC-DAD-ESI/MS analysis

The aim of this study was to isolate and identify the anthocyanins in the black seed coated soybean (cv. Cheongja 3, Glycine max (L.) Merr.) using reverse phase C-18 open column chromatography and high-performance liquid chromatography (HPLC) with diode array detection and electro spray ionization/mass spectrometry (DAD-ESI/MS) analysis, respectively. Anthocyanins were extracted from the coat of black soybeans with 1% TFA in methanol, isolated by RP-C-18 column chromatography, and their structures elucidated by 1D and 2D NMR spectroscopy. The isolated anthocyanins were characterised as delphinidin-3-O-glucoside (3), cyanidin-3-O-glucoside (5), petunidin-3-O-glucoside (6), pelargonidin-3-O-glucoside (7) and cyanidin (9). Furthermore, four minor anthocyanins were detected and identified as catechin-cyanidin-3-O-glucoside (1), delphinidin-3-O-galactoside (2), cyanidin-3-O-galactoside (4), and peonidin-3-O-glucoside (8) based on the fragmentation patterns of HPLC-DAD-ESI/MS analysis.     

Effects of pectolytic enzyme treatments on anthocyanins in raspberry juice

Raspberry juices treated with two commercial pectinase preparations lost almost 20% of their total anthocyanin pigments; losses were related to both concentration of enzyme and time of treatment. Analysis of individual anthocyanins showed differences between the enzymes. Ultrazyme reduced all components in similar proportions, whereas Pectinex apparently also converted cyanidin-3-sophoroside and cyanidin-3-glucosylrutinoside into cyanidin-3-glucoside and cyanidin-3-rutinoside respectively, presumably by hydrolysis of β1–2 glucosidic bonds by glucosidase present in the Pectinex.     

Phenolic Compounds from the Leaves of Vitis labrusca and Vitis vinifera L. as a Source of Waste Byproducts: Development and Validation of LC Method and Antichemotactic Activity

The cultivation of Vitis (Vitaceae) grape varieties is one of the most important economic activities in agribusiness in southern Brazil. Vitis varieties are rich in polyphenolic compounds with several pharmacological and biological activities, such as antioxidant action. In this context, this study analyzed qualitatively and quantitatively the anthocyans and flavonoids found in the leaves of grape varieties Vitis vinifera and Vitis labrusca. For this purpose, vine leaf extracts were prepared and the chemical profile of each was characterized by LC/MS-MS. Two high performance liquid chromatography-validated methods were performed using UV/VIS-LC-DAD detector to quantify phenolic compounds. The main anthocyanins isolated from vine leaves were cyanidin-3-O-glucoside and peonidin-3-O-glucoside. The flavonoids identified were rutin, quercetin-3-O-galactoside, quercetin-3-O-glucoside, and quercetin-3-O-glucuronide, which was the predominant compound. The Waters X-Terra® RP18 column allowed the effective separation of quercetin-3-O-glucuronide from the other flavonoids for the first time, besides the partial separation of quercetin-3-O-galactoside from quercetin-3-O-glucoside. Furthermore, another phenolic compound was confirmed by MS spectrometry, using direct infusion, as being trans-caftaric acid. The present study also investigates the antichemotactic activity in vitro of grape crude extracts, fractions, and isolated compounds. It was demonstrated that almost all fractions and isolated compounds showed increased antichemotactic effect in response to LPS with a more pronounced values of IC₅₀ for anthocyanins fraction, rutin, quercetin-3-O-galactoside, and trans-caftaric acid (0.9, 1.6, 3.7, and 5.1 ng/mL, respectively).